This invention relates to a process for producing an epoxy compound represented by the following general formula (4): 
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form.)
This invention also relates to a fragrance-, flavor- or scent-imparting composition containing said epoxy compound, and also to drinks and foods, perfumes, cosmetics and tobaccos respectively containing said compound.
The novel fragrance-, flavor- or scent-imparting composition containing said epoxy compound and foods and drinks, perfumes, cosmetics and tobaccos respectively containing said composition are intensified in fruity, camphoric, floral, amber or woody fragrance, flavor or scent.
Among the compounds represented by the general formula (4), 1-vinyl-13-oxabicyclo[10.1.0]tridecane is a publicly known chemical substance, and it is a useful compound for producing 5-cyclohexadecenone. The method of using the epoxy compound is described in JP 49-47345, A Gazette.
However, the fragrant properties of these epoxy compounds have not been recognized so far. Of course, there is no report about the use of them as fragrance-, flavor- or scent-imparting compositions and foods and drinks, perfumes, cosmetics and tobaccos respectively containing said compositions.
It is only known that 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene as an epoxy compound similar to the epoxy compounds represented by the general formula (4) has a woody amber fragrance.
As a method of synthesizing the 1-vinyl-13-oxabicyclo[10.1.0]tridecane, for example, disclosed is a process comprising the steps of letting vinylmagnesium chloride act on 2-chlorocyclododecanone, to make chlorohydrin, and cyclizing using sodium hydroxide or sodium methoxide as a base, as shown in the following reaction formula (xe2x80x9cSynthetic Perfume Chemistry and Knowledge on Commercial Products (in Japanese)xe2x80x9d, Yukagaku, 1974, Vol. 23, No. 6, Page 371). However, it does not describe anything at all about the stereochemistry of the obtained product. 
However, the process for producing said epoxy compound has the following problem: the solvent must be once recovered after production of chlorohydrin, to increase the number of production steps; the cyclization reaction using sodium hydroxide as a base requires a long time and is low in yield; and sodium methoxide is relatively expensive and the treatment of the waste liquid after completion is difficult industrially disadvantageously.
On the other hand, it is general that compounds used as perfumes are quite different in fragrance even if they are slightly different in structure. So, it is very important for obtaining novel fragrances, to synthesize various compounds for examining their fragrances. Furthermore, the materials to be mixed are required to satisfy various demands such as low prices and unique fragrances. Numerous perfume materials that have a fruity, camphoric, floral, amber or woody fragrance are known, but the fashion of fragrances keeps changing with the age. So, it is very important to find novel perfume materials.
An object of this invention is to provide a process for producing an epoxy compound with said performance industrially advantageously at low cost in a short process.
Another object of this invention is to provide a novel fruity, camphoric, floral, amber or woody fragrance-, flavor- or scent-imparting composition, and foods and drinks, perfumes, cosmetics and tobaccos respectively containing said composition.
The inventors studied intensively to solve the problems of the conventional methods as described above, and found that epoxy compounds can be easily produced by means of a specific process. Thus, this invention has been completed.
The first subject matter of this invention is a process for producing an epoxy compound represented by the following general formula (4) 
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and transform), comprising the steps of letting an xcex1-halocyclododecanone represented by the following general formula (1) 
(where X1 denotes chlorine, bromine or iodine) and an organic magnesium compound represented by the following general formula (2)
R1MgX1xe2x80x83xe2x80x83(2)
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and X1 denotes chlorine, bromine or iodine) react with each other for Grignard reaction, hydrolyzing to obtain a halohydrin represented by the following general formula (3) 
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms; X1 denotes chlorine, bromine or iodine; and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form), and letting the halohydrin and a base react with each other in the presence of an phase transfer catalyst.
The second subject matter of this invention is a process for producing a compound represented by said general formula (4), comprising the steps of letting an xcex1-halocyclododecanone represented by the following general formula (1) 
(where X1 denotes chlorine, bromine or iodine) and an organic magnesium compound represented by the following general formula (2)
R1MgX1xe2x80x83xe2x80x83(2)
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and X1 denotes chlorine, bromine or iodine) react with each other for Grignard reaction, and adding an aprotic polar solvent, for epoxidation.
The third subject matter of this invention is a novel fruity, camphoric, floral, amber or woody fragrance-, flavor- or scent-imparting composition containing an epoxy compound represented by said general formula (4), and foods and drinks, perfumes, cosmetics and tobaccos respectively containing said composition.
At first, an epoxy compound represented by said general formula (4) can be synthesized according to either of the following two processes. 
(where R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms, and the wavy line denotes cis form, trans form or a mixture consisting of cis form and trans form).
In the first synthesizing process, an xcex1-haloketone represented by the formula (1) and an organic magnesium compound represented by the formula (2) are made to react with each other for Graignard reaction, to produce an alkoxymagnesium halide represented by the formula (5), and a hydrogen ion donor is added for hydrolysis, to produce chlorohydrin represented by the formula (3). Then, a base is caused to act on it in the presence of an phase transfer catalyst, for epoxidation reaction, to form an epoxy compound represented by the formula (4).
In the second process, an xcex1-haloketone represented by the formula (1) and an organic magnesium compound represented by the formula (2) are made to react with each other for Grignard reaction, to produce an alkoxymagnesium halide represented by the formula (5), and an aprotic polar solvent is added for cyclization reaction, to form an epoxy compound represented by the formula (4).
In the organic magnesium compound represented by the formula (2), R1 denotes an alkyl group with 1 to 5 carbon atoms, alkenyl group with 2 to 5 carbon atoms or alkynyl group with 2 to 5 carbon atoms. Alkyl groups with 1 to 5 carbon atoms include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, pentyl group, 1,2-diemthylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, etc., though not limited thereto in this invention. Alkenyl groups with 2 to 5 carbon atoms include a vinyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methylpropenyl group, allyl group, 1,1-dimethylallyl group, etc., though not limited thereto in this invention. Alkynyl groups with 2 to 5 carbon atoms include an ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group and 4-pentynyl group, though not limited thereto in this invention. X1 denotes a halogen atom such as a chlorine atom, bromine atom or iodine atom.
The amount of the organic magnesium compound used in this invention is one equivalent or more for each equivalent of the substrate, and a preferable range is 1.1 to 3.0 equivalents.
The solvents that can be used in the Grignard reaction between the xcex1-haloketone represented by the formula (1) and the organic magnesium compound represented by the formula (2) include ether compounds such as diethyl ether and tetrahydrofuran, aliphatic hydrocarbon compounds such as petroleum ether and cyclohexane, aromatic compounds such as benzene, toluene and xylene, and halogen compounds such as chloroform, dichloromethane and dichloroethane.
These solvents can also be used as a mixture obtained by mixing them at a desired ratio. Among them, tetrahydrofuran and toluene are especially preferable. The used amount of the solvent is usually 100 to 5000 wt %, preferably 500 to 2000 wt % based on the weight of the substrate.
It is preferable that the reaction temperature of the Grignard reaction between the xcex1-haloketone represented by the formula (1) and the organic magnesium compound represented by the formula (2) is xe2x88x9220 to 30xc2x0 C. A more preferable range is 0 to 20xc2x0 C. It is preferable that the reaction time is 0.5 to 3 hours. A more preferable range is 1 to 2 hours.
The hydrogen ion donors that can be used for hydrolyzing the alkoxymagnesium halide represented by the formula (5) include water, mineral acid aqueous solutions such as hydrochloric acid aqueous solution and sulfuric acid aqueous solution, organic acid aqueous solutions such as formic acid aqueous solution, oxalic acid aqueous solution and acetic acid aqueous solution, ammonium chloride aqueous solution, etc. Among them, hydrochloric acid aqueous solution is especially preferable.
After the alkoxymagnesium halide is hydrolyzed, the solution is separated to take out the organic layer, and the organic layer is preferably washed with an alkali and used for the subsequent epoxidation reaction.
The phase transfer catalysts that can be used in this invention include phosphonium, sulfonium and ammonium compounds. Preferably ammonium compounds can be used and they can be represented by the following general formula (6).
R2R3R4R5NX2xe2x80x83xe2x80x83(6)
(where R2 to R5 denote, respectively independently, an alkyl group with 1 to 11 carbon atoms or benzyl group, and X2 denotes a iodide, bromide, chloride, hydroxide or hydrogensulfate). The ammonium compounds include, for example, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammoniumbromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide, trioctylmethylammonium chloride, tetrabutylammonium hydrogensulfate, tetrabutylammonium hydroxide, etc. As the phase transfer catalyst, a polymer support ammonium compound can also be used.
The used amount of the phase transfer catalyst can be 0.01 mol % or more based on the amount of the substrate. A preferable range is 0.1 to 30 mol %.
The bases that can be used in the cyclization reaction of the chlorohydrin represented by the formula (3) include alkali metal hydroxides and alkali metal carbonates. Preferable are sodium hydroxide, potassiumhydroxide, lithiumhydroxide, sodiumcarbonate, potassium carbonate and lithium carbonate. The used amount of the base can be 1 equivalent or more for each equivalent of the substrate, though depending on the reacting substrate. A preferable range is 2 to 5 equivalents. The base is usually used as an aqueous solution. A higher base concentration is more advantageous for the reaction. A preferable concentration range is 5 to 50%. The used amount of the base aqueous solution is usually 100 to 5000 wt % based on the weight of the substrate. A preferable range is 300 to 2000 wt %.
In the cyclization reaction of chlorohydrin represented by the formula (3), it is preferable that the reaction temperature is 0 to 120xc2x0. A more preferable range is 80 to 110xc2x0 C. Furthermore, it is preferable that the reaction time is 1 to 24 hours. A more preferable range is 2 to 12 hours.
The aprotic polar solvents that can be added to the alkoxymagnesium halide represented by the formula (5) produced by the Grignard reaction between the xcex1-haloketone represented by the formula (1) and the organic magnesium compound represented by the formula (2) include N,Nxe2x80x2-dimethylpropyleneurea (DMPU), 1,3-dimethyl-2-imidazolidinone (DMI), hexamethylphosphoric acid triamide (HMPA), DMSO, DMF, 1,1,3,3-tetramethylurea (TMU), 1-methyl-2-pyrrolidinone (NMP), etc. In view of reactivity, safety, price, etc., DMPU and DMI can be especially preferably used. It is preferable that the added amount of the aprotic polar solvent is 2 to 10 equivalents for each equivalent of the organic magnesium compound. A more preferable range is 3 to 5 equivalents.
It is preferable that the reaction temperature after adding the aprotic polar solvent is 20 to 100xc2x0 C. A more preferable range is 40 to 80xc2x0 C. Furthermore, it is preferable that the reaction time is 30 minutes to 24 hours. A more preferable range is 1 to 12 hours.
As the epoxy compound represented by said general formula (3) obtained in this invention, two isomers of cis form and trans form attributable to epoxy groups exist, and both the isomers can be used at a desired ratio from 0 to 100 respectively. The epoxy compound has a very strong and sustainable fruity, camphoric, floral, amber or woody fragrance. Especially 1-vinyl-13-oxabicyclo[10.1.0]tridecane which is an epoxy compound having a vinyl group as R1 of the general formula (3) has a very strong amber scent, and its cis isomer has a very diffusive woody, amber and sandalwood-like fragrance. On the other hand, the trans isomer has a strong woody animal scent.
The epoxy compound obtained in this invention can be used as a fragrance-, flavor- or scent-imparting composition (flavor and fragrance composition) singly or as a mixture with another ingredient such as a perfume. The flavor and fragrance composition can be added to foods and drinks, perfumes, cosmetics and tobaccos. The perfume composition can contain any ingredient used in ordinary perfumes without any restriction.
When the epoxy compound of this invention is used to produce a flavor and fragrance composition, the added amount can be selected usually in a range of 0.01 to 30 parts by weight, but depending on the intended sensory effect, an amount outside this range can also be used.
Furthermore, the epoxy compound obtained in this invention can be added as a fragrance-, flavor- or scent-imparting flavor and fragrance composition to various foods and drinks, perfumes, cosmetics and tobaccos, for giving the fragrance, flavor to scent peculiar to the epoxy compound. The amount of the epoxy compound of this invention added to various foods and drinks, perfumes, cosmetics and tobaccos can be adequately selected depending on the kinds of the foods and drinks, perfumes, cosmetics and tobaccos to which it is added.
The fragrance-, flavor- or scent-imparting perfume composition containing the epoxy compound of this invention can be added without any particular restriction to any various foods and drinks, perfumes, cosmetics and tobaccos desired to be given the fragrance-, flavor- or scent-imparting effect of the perfume composition. For example, it can be used for giving a fragrance to a wide range of products such as soaps, shampoos, cosmetics, sprays, aromatics, deodorants, washing agents and textile softeners, and also for producing base materials of perfumes. Furthermore, it can be added to strongly carbonated, weakly carbonated or non-carbonated beverages such as fruit drinks, fruit wine and milk drinks, ices such as ice creams and sherbets, Japanese and Western confectionaries, favorite foods such as jams, chewing gums, tea, coffee, cocoa and green tea, other food additives, animal feeds, etc.
For tobaccos, it can be added to cigarettes, pipe tobaccos and cigars respectively produced from ordinary leaf tobaccos, and synthetic tobaccos produced using natural fibers or tissue-cultured plants. In the case of cigarettes, even if it is added to the materials used for producing tobaccos such as paper, glue, filters and the like, the intended scent-imparting effect can be obtained. Other applications include various health and sanitation materials such as disinfectants, and taste improvers and flavors to facilitate the administration of drugs.